A nanoprobe for ratiometric imaging of glutathione in living cells based on the use of a nanocomposite prepared from dua

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ORIGINAL PAPER

A nanoprobe for ratiometric imaging of glutathione in living cells based on the use of a nanocomposite prepared from dual-emission carbon dots and manganese dioxide nanosheets Zhiwei Deng 1 & Xiufang Li 1 & Hui Liu 1 & Yao He 1 & Jie Zhang 1 & Jing Yuan 1 & Peiru Gao 1 & Xuling Jiang 1 & Yanjing Yang 1 & Shian Zhong 1 Received: 17 November 2019 / Accepted: 18 August 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020

Abstract A ratiometric fluorescence assay for glutathione (GSH) was developed. The novel assay is based on a nanoprobe composed of manganese dioxide nanosheets (MnO2 NS) and dual-emission carbon dots (de-CDs) with intrinsic GSH-response property. After construction of the nanoprobe, two emission peaks of de-CDs were suppressed to varying degrees by MnO2 NS. The suppression was relieved and the two emission peaks recovered proportionally when MnO2 NS was decomposed by GSH, thus realizing the ratiometric assay for micromolar GSH. The intrinsic responsiveness of de-CDs to millimolar GSH broadens the analytical range of the nanoprobe. An appropriate precursor, calcon-carboxylic acid, was screened out to synthesize de-CDs via one-step hydrothermal treatment. The de-CD@MnO2 NS nanoprobe can measure GSH concentrations through the fluorescence intensity ratio between 435 and 516 nm excited at 365 nm. The range of response was from 1 μM to 10 mM and the detection limit reached 0.6 μM (3σ criterion). Benefiting from its good biocompatibility, the proposed nanoprobe has excellent applicability for intracellular GSH imaging. Keywords Fluorescence nanomaterial . Fluorescence ratio . Intracellular imaging . Nanodevices . Hydrothermal treatment . Inner filter effect . Fluorescence resonance energy transfer

Introduction Glutathione (GSH) is a major nonprotein thiol which plays important roles in various biological functions, such as the cellular antioxidant defense system, gene regulation, xenobiotic metabolism, and intracellular signal transduction [1–3]. The changes in GSH level are related to many diseases, including leucocyte loss, diabetes, Alzheimer’s disease, and Parkinson’s [4–6]. Thus, knowledge of the levels of GSH in living cells is crucial for illustrating its accurate cell functions Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-04495-1) contains supplementary material, which is available to authorized users. * Yanjing Yang [email protected] * Shian Zhong [email protected] 1

College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China

as well as providing pivotal assistance for early diagnosis of diseases. A variety of analytical techniques have been developed for measuring GSH level for biomedical applications [7–12]. Among different kinds of GSH assays, optical methods based on fluorescence techniques have attracted more interest because of the advantages of high sensitivity, spatial resolving power, nondestructiveness, and ease of miniaturization.